CN114843504A - Single-crystal-morphology lithium ion battery ternary positive electrode material and preparation method and application thereof - Google Patents
Single-crystal-morphology lithium ion battery ternary positive electrode material and preparation method and application thereof Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 30
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000013078 crystal Substances 0.000 claims abstract description 28
- 239000000654 additive Substances 0.000 claims abstract description 26
- 230000000996 additive effect Effects 0.000 claims abstract description 26
- 239000010406 cathode material Substances 0.000 claims abstract description 25
- 229910013716 LiNi Inorganic materials 0.000 claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 3
- 239000011572 manganese Substances 0.000 claims description 46
- 239000000243 solution Substances 0.000 claims description 43
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 27
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- 239000012266 salt solution Substances 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 15
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- 238000005086 pumping Methods 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000012716 precipitator Substances 0.000 claims description 12
- 238000005245 sintering Methods 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 8
- 239000010405 anode material Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 6
- 229940044175 cobalt sulfate Drugs 0.000 claims description 6
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 6
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 150000002696 manganese Chemical class 0.000 claims description 6
- 229940099596 manganese sulfate Drugs 0.000 claims description 6
- 235000007079 manganese sulphate Nutrition 0.000 claims description 6
- 239000011702 manganese sulphate Substances 0.000 claims description 6
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 101100496858 Mus musculus Colec12 gene Proteins 0.000 claims description 4
- 150000003841 chloride salts Chemical group 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 5
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 238000001000 micrograph Methods 0.000 description 5
- 229940053662 nickel sulfate Drugs 0.000 description 5
- 239000011163 secondary particle Substances 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 2
- 229910016722 Ni0.5Co0.2Mn0.3 Inorganic materials 0.000 description 1
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a high-voltage type single crystal morphology lithium ion battery ternary positive electrode material and a preparation method and application thereof. The chemical general formula of the ternary cathode material is LiNi x Co y Mn 1‑x‑y A a O 2 Wherein x is more than or equal to 0.5<1，0<y≤0.5，0<x+y≤0.5，0<a is less than or equal to 0.01, and the additive modified element A is at least one of Mg, Ca and Sr. The ternary cathode material provided by the invention has a single crystal morphology, can avoid the occurrence of particle fracture in a circulation process, relieves the side reaction with electrolyte, improves the stability, and improves the circulation performance of the ternary cathode material under high cut-off voltage (4.5V). The additive is used as a modification element, can effectively promote the formation of single crystal morphology, and can improve the cycling stability of the material.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery electrode materials, and particularly relates to a lithium ion battery ternary cathode material with a single crystal morphology, and a preparation method and application thereof.
Background
Lithium Ion Batteries (LIBs) have dominated the field of mobile electronic devices. Among all the components of lithium ion batteries, the positive electrode material plays a very important role, which determines the electrochemical performance and cost of the battery. Layered lithium nickel cobalt manganese LiNi 1-x-y Co x Mn y O 2 The (NCM) ternary positive electrode material has the advantages of high specific capacity, high discharge voltage, high energy density, good rate capability and the like, can provide long endurance mileage and high charging speed for new energy automobiles, and becomes one of the mainstream power battery positive electrode materials.
At present, the appearance of the traditional commercial NCM positive electrode material is spherical secondary particles with the diameter of about 10 μm, and the secondary particles are formed by tightly agglomerating nano or submicron primary particles. However, the spherical secondary particles of such morphology are easily broken during the rolling process of the pole piece, or broken during repeated cycles, so that the electrochemical performance is degraded.
Disclosure of Invention
The invention provides a single-crystal-morphology lithium ion battery ternary positive electrode material with high tap density, excellent processability, slower capacity fading and excellent electrochemical performance at high temperature or high voltage, and a preparation method and application thereof.
The lithium ion battery ternary cathode material with the single crystal morphology has a chemical general formula of LiNi x Co y Mn 1-x-y A a O 2 Wherein x is more than or equal to 0.5<1，0<y≤0.5，0<x+y≤0.5，0<a is less than or equal to 0.01; a is at least one of additive modified elements Mg, Ca and Sr; the median particle diameter D50 of the single-crystal-morphology lithium ion battery ternary positive electrode material is 1-10 mu m.
Preferably, the median particle diameter D50 of the lithium ion battery ternary positive electrode material with the single crystal morphology is 3-5 μm.
The preparation method of the single-crystal-morphology lithium ion battery ternary cathode material provided by the invention comprises the following steps of:
1) preparing a metal salt solution: weighing nickel salt, cobalt salt and manganese salt according to the molar ratio x: y (1-x-y), dissolving the nickel salt, cobalt salt and manganese salt in deionized water, and uniformly mixing to obtain a metal salt solution; preparing a precipitator, an additive solution and a base solution;
2) pumping the metal salt solution, the precipitating agent and the additive solution in the step 1) into the substrate in the step 1), reacting at a proper temperature, pH and stirring speed, and after the reaction is finished, aging, washing and drying to obtain a carbonate precursor Ni x Co y Mn 1-x-y A a CO 3 ；
3) The carbonate precursor Ni prepared in the step 2) is added x Co y Mn 1-x-y A a CO 3 Uniformly mixing with a lithium source, sintering in an oxygen atmosphere furnace, cooling, grinding, crushing and sieving to obtain the lithium ion battery ternary cathode material LiNi with the single crystal morphology x Co y Mn 1-x-y A a O 2 。
Preferably, in the step 1), the nickel salt is at least one of nickel sulfate, nickel nitrate and nickel chloride; the cobalt salt is at least one of cobalt sulfate, cobalt nitrate and cobalt chloride; the manganese salt is at least one of manganese sulfate, manganese nitrate and manganese chloride; the total concentration of metal cations in the metal salt solution is 0.5-2.0 mol/L.
Preferably, in the step 1), the precipitant is Na with a concentration of 1-3 mol/L 2 CO 3 、NH 4 HCO 3 And NH 3 ·H 2 One or a mixture of O solution, wherein the mixture is composed of Na with the concentration of 1-3 mol/L 2 CO 3 、NH 4 HCO 3 And NH 3 ·H 2 The O solution is composed of 1-200: 1-200 by volume ratio; the additive is chloride salt of a modifying element A, and the chloride salt of the modifying element A is MgCl 2 、CaCl 2 And SrCl 2 At least one additive, wherein the concentration of the additive is 0.01-1 mol/L; the base solution is composed of deionized water and NH with the concentration of 1-3 mol/L 4 HCO 3 And NH 3 ·H 2 The O solution is prepared according to the volume ratio of 1-200: 1-200.
Preferably, in the step 2), the pumping speed of the metal salt solution, the precipitator and the additive solution is 1-100 mL/min respectively, the pumping time is the same as the reaction time, and the metal salt solution, the precipitator and the additive solution are pumped continuously within the reaction time; the reaction temperature is 30-60 ℃, the pH value is 7-9, the stirring speed is 300-900 r/min, the reaction time is 8-48 h, the aging time is 6-16 h, the mixture is washed by deionized water at 50-90 ℃, the drying temperature is kept at 60-150 ℃, and the drying time is 6-20 h.
Preferably, in the step 2), Ni x Co y Mn 1-x-y A a CO 3 The content a of the additive element A is 0.001-0.01.
Preferably, in the step 3), the lithium source is at least one of lithium carbonate, lithium hydroxide and lithium nitrate; carbonate precursor Ni x Co y Mn 1-x-y A a CO 3 The molar ratio of the Li/(Ni + Co + Mn) in the lithium source to the Li/(Ni + Co + Mn) is 1.00-1.10; carbonate precursor Ni x Co y Mn 1-x-y A a CO 3 Mixing the lithium source and the lithium source in a high-speed mixer at a rotating speed of 400-800 r/min for 30-60 min.
Preferably, in the step 3), the sintering process is as follows: the temperature rising speed is 1-10 ℃/min, the first-stage sintering temperature is 500-700 ℃, and the sintering time is 4-10 h; and then the temperature is raised to the second-stage sintering temperature of 800-1000 ℃, and the sintering time is 8-14 h.
The invention provides an application of the lithium ion battery ternary cathode material with the single crystal morphology in a lithium ion battery.
The invention has the beneficial effects that:
(1) the preparation method has the characteristics of simple preparation process, easy control of preparation process participation, compatibility with the existing preparation equipment of the ternary cathode material, and easy industrial popularization.
(2) LiN prepared by the inventioni x Co y Mn 1-x-y A a O 2 The anode material has a single crystal shape, the single crystal grains are uniformly distributed, the primary particle size is micron-sized, the median particle size D50 is 1-10 mu m, and the particle size is easy to control.
(3) The single crystal LiNi prepared by the invention x Co y Mn 1-x-y A a O 2 The anode material has a standard layered structure, can effectively avoid the phenomenon that particles of the material are broken in the circulating process, relieve the side reaction with electrolyte, improve the stability and improve the circulating performance of the anode material under the condition of high cut-off voltage of 4.5V.
Drawings
FIG. 1 is a view showing a single-crystal LiNi product obtained in example 1 0.5 Co 0.2 Mn 0.3 Sr 0.005 O 2 The magnification of the scanning electron microscope image of the anode material is 2000 times;
FIG. 2 is a view showing a single crystal LiNi as a product of example 2 0.6 Co 0.2 Mn 0.2 Ca 0.006 O 2 The magnification of the scanning electron microscope image of the anode material is 2000 times;
FIG. 3 is a view showing a single-crystal LiNi product obtained in example 3 0.83 Co 0.12 Mn 0.05 Mg 0.003 Sr 0.003 O 2 The magnification of the scanning electron microscope image of the anode material is 2000 times;
FIG. 4 is a view showing a single-crystal LiNi as a product in comparative example 1 0.83 Co 0.11 Mn 0.06 O 2 The magnification of the scanning electron microscope image of the anode material is 2000 times;
FIG. 5 shows LiNi, a single crystal, which is a product of example 1 0.5 Co 0.2 Mn 0.3 Sr 0.005 O 2 4.5V cycle curve for positive electrode material;
FIG. 6 shows LiNi, a single crystal obtained in example 2 0.6 Co 0.2 Mn 0.2 Ca 0.006 O 2 4.5V cycle curve for positive electrode material;
FIG. 7 shows a single-crystal LiNi as a product of example 3 0.83 Co 0.12 Mn 0.05 Mg 0.003 Sr 0.003 O 2 4.5V cycle curve for positive electrode material;
FIG. 8 is a view showing a single-crystal LiNi product in comparative example 1 0.83 Co 0.11 Mn 0.06 O 2 4.5V cycling profile of the positive electrode material.
Detailed Description
To further illustrate the technical means of the present invention to achieve the intended purpose, the present invention will be further described in detail with reference to the accompanying drawings and examples. It should be understood that the following examples are only for further illustration of the present invention and are not intended to limit the present invention, and the examples of the present invention are not limited to the following examples.
The materials referred to in the following examples and comparative examples are commercially available.
The percentages in the following examples and comparative examples are, unless otherwise specified, all molar percentages.
Example 1
(1) Weighing nickel sulfate, cobalt sulfate and manganese sulfate according to the proportion of n (Ni), n (Co), n (Mn) and 2:3 to prepare a metal salt solution, wherein the total concentration of metal cations is 1 mol/L; na with the concentration of 1.5mol/L 2 CO 3 、NH 4 HCO 3 And NH 3 ·H 2 Mixing the O solution in a volume ratio of 120:1:1 to prepare a precipitator; SrCl with the preparation concentration of 0.1mol/L 2 The solution is used as an additive solution; preparing NH with the concentration of 1.5mol/L 4 HCO 3 And NH 3 ·H 2 And preparing the solution O and deionized water into a base solution according to the volume ratio of 120:1: 1.
(2) Adding 5L of the base solution into a reaction kettle, synchronously pumping the metal salt solution at the speed of 15mL/min, the precipitator at the speed of 10mL/min and the additive solution at the speed of 1mL/min into the reaction kettle for the same time as the reaction time, continuously pumping in the reaction time, keeping the reaction temperature at 50 ℃, the pH value at 7.6 and the stirring speed at 800r/min, aging for 14h after reacting for 30h, washing with 70 ℃ deionized water, and drying for 12h at 90 ℃ to obtain a carbonate precursor Ni precursor 0.5 Co 0.2 Mn 0.3 Sr 0.005 CO 3 。
(3) The prepared carbonate precursor Ni 0.5 Co 0.2 Mn 0.3 Sr 0.005 CO 3 Mixing the lithium carbonate and the lithium carbonate in a high-speed mixer according to the molar ratio of Li/(Ni + Co + Mn) of 1.05 at the speed of 600r/min for 60min, putting the mixture into a tubular atmosphere furnace after uniformly mixing, introducing oxygen atmosphere, heating to 650 ℃ at the temperature rising speed of 5 ℃/min, preserving heat for 4h, then heating to 970 ℃ at the temperature rising speed of 5 ℃/min, preserving heat for 12h, and cooling to room temperature along with the furnace. The product was ground, crushed and sieved to obtain high voltage single crystal LiNi with a median particle size D50 of 5.6 μm 0.5 Co 0.2 Mn 0.3 Sr 0.005 O 2 And (3) a positive electrode material.
Example 2
(1) Weighing nickel sulfate, cobalt sulfate and manganese sulfate according to the proportion of n (Ni), n (Co), n (Mn) and 2:2 to prepare a metal salt solution, wherein the total concentration of metal cations is 1 mol/L; na with the concentration of 2.0mol/L 2 CO 3 、NH 4 HCO 3 And NH 3 ·H 2 Mixing the O solution in a volume ratio of 100:1:1 to prepare a precipitator; CaCl with the concentration of 0.15mol/L is prepared 2 The solution is used as an additive solution; NH with the concentration of 2.0mol/L 4 HCO 3 And NH 3 ·H 2 And preparing the solution O and deionized water into a base solution according to the volume ratio of 120:1: 1.
(2) Adding 5L of the base solution into a reaction kettle, synchronously pumping the metal salt solution at the speed of 20mL/min, the precipitator at the speed of 10mL/min and the additive solution at the speed of 1.5mL/min into the reaction kettle for the same time as the reaction time, continuously pumping in the reaction time, keeping the reaction temperature at 45 ℃, the pH value at 7.8, stirring at the speed of 750r/min, aging for 12h after 36h of reaction, washing with 80 ℃ deionized water, and drying at 120 ℃ for 10h to obtain a carbonate precursor Ni precursor 0.6 Co 0.2 Mn 0.2 Ca 0.01 CO 3 。
(3) The prepared carbonate precursor Ni 0.6 Co 0.2 Mn 0.2 Ca 0.006 CO 3 Mixing with lithium hydroxide at the molar ratio of Li/(Ni + Co + Mn) of 1.06 in a high-speed mixer at the speed of 500r/min for 50min, and putting the mixture into a tubular gasAnd introducing oxygen atmosphere into the atmosphere furnace, heating to 680 ℃ at the heating rate of 3 ℃/min, preserving heat for 10h, then heating to 940 ℃ at the heating rate of 3 ℃/min, preserving heat for 10h, and cooling to room temperature along with the furnace. The product was ground, crushed and sieved to obtain high voltage single crystal LiNi with a median particle size D50 of 3.7 μm 0.6 Co 0.2 Mn 0.2 Ca 0.006 O 2 And (3) a positive electrode material.
Example 3
(1) Weighing nickel sulfate, cobalt sulfate and manganese sulfate according to the proportion of n (Ni), n (Co), n (Mn) 83:12:5 to prepare a metal salt solution, so that the total concentration of metal cations is 1.5 mol/L; na with the concentration of 2.5mol/L 2 CO 3 、NH 4 HCO 3 And NH 3 ·H 2 Mixing the O solution according to the volume ratio of 125:1:1 to prepare a precipitator; MgCl with the concentration of 0.1mol/L is prepared 2 And SrCl 2 The solution is used as an additive solution; adding NH with the concentration of 2.5mol/L 4 HCO 3 And NH 3 ·H 2 And preparing the O solution and deionized water into a base solution according to the volume ratio of 125:1: 1.
(2) Adding 5L of the base solution into a reaction kettle, synchronously pumping the metal salt solution into the reaction kettle at the speed of 20mL/min, the precipitator at the speed of 12mL/min and the additive solution at the speed of 1.5mL/min for the same time as the reaction time, continuously pumping in the reaction time, keeping the reaction temperature at 55 ℃, the pH at 7.5 and the stirring speed at 750r/min, aging for 12h after reacting for 32h, washing with 80 ℃ deionized water, and drying for 12h at 80 ℃ to obtain a carbonate precursor Ni precursor 0.83 Co 0.1 2 Mn 0.05 Mg 0.003 Sr 0.003 CO 3 。
(3) Mixing the prepared carbonate precursor and lithium hydroxide in a high-speed mixer according to the molar ratio of Li/(Ni + Co + Mn) of 1.04 at a speed of 600r/min for 45min, uniformly mixing, putting the mixture into a tubular atmosphere furnace, introducing oxygen atmosphere, heating to 700 ℃ at a heating rate of 6 ℃/min, preserving heat for 6h, heating to 850 ℃ at a heating rate of 6 ℃/min, preserving heat for 12h, and cooling to room temperature along with the furnace. Grinding, crushing and sieving the product to obtain the median particle sizeHigh-voltage single-crystal LiNi with D50 of 4.3 μm 0.83 Co 0.12 Mn 0.05 Mg 0.003 Sr 0.003 O 2 And (3) a positive electrode material.
Comparative example 1
(1) Weighing nickel sulfate, cobalt sulfate and manganese sulfate according to the proportion of n (Ni), n (Co), n (Mn) 83:11:6 to prepare a metal salt solution, wherein the total concentration of metal cations is 1.0 mol/L; na with the concentration of 1.5mol/L 2 CO 3 、NH 4 HCO 3 And NH 3 ·H 2 Mixing the O solution according to the volume ratio of 75:1:1 to prepare a precipitator; NH with the concentration of 1.5mol/L 4 HCO 3 And NH 3 ·H 2 And preparing the solution O and deionized water into a base solution according to the volume ratio of 75:1: 1.
(2) Adding 5L of the base solution into a reaction kettle, synchronously pumping the metal salt solution into the reaction kettle at the speed of 15mL/min and the precipitator at the speed of 10mL/min, wherein the pumping time is the same as the reaction time, continuously pumping in the reaction time, keeping the reaction temperature at 55 ℃, the pH at 7.6, stirring at the speed of 750r/min, aging for 16h after reacting for 28h, washing with 80 ℃ deionized water, and drying at 80 ℃ for 16h to obtain a carbonate precursor Ni 0.83 Co 0.11 Mn 0.06 CO 3 。
(3) Mixing the prepared carbonate precursor and lithium hydroxide in a high-speed mixer according to the molar ratio of Li/(Ni + Co + Mn) of 1.05 at a speed of 600r/min for 30min, uniformly mixing, putting the mixture into a tubular atmosphere furnace, introducing oxygen atmosphere, heating to 500 ℃ at a heating speed of 5 ℃/min, preserving heat for 4h, heating to 800 ℃ at a heating speed of 5 ℃/min, preserving heat for 14h, and cooling to room temperature along with the furnace. Grinding, crushing and sieving the product to obtain LiNi 0.83 Co 0.11 Mn 0.06 O 2 And (3) a positive electrode material.
The positive electrode materials obtained in examples 1 to 3 and comparative example 1 were subjected to morphology analysis by using a scanning electron microscope to obtain scanning electron microscope images, as shown in fig. 1 to 4.
The cathode materials obtained in examples 1-3 and comparative example 1 were assembled into button cells using a technical method for preparing a lithium ion button cell from the cathode material, which is well known to those skilled in the art, and electrochemical performance tests were performed on a blue test system, and the results are shown in table 1.
TABLE 1 electrochemical performance of button cell (2.8-4.5V, 25 deg.C)
Table 1 lists electrochemical performance data of the cathode materials prepared in examples 1 to 3 and comparative example 1, and it can be found that, compared with comparative example 1, the cathode materials prepared in examples 1 to 3 have advantages in specific discharge capacity, first coulombic efficiency, capacity retention rate, and the like.
As can be seen from fig. 1 to 3, the cathode material prepared by the method of the present invention has a dispersed micron-sized single crystal morphology, while the cathode material prepared in comparative example 1 is an agglomerated secondary spherical particle; the electrochemical performance of the material is optimized in the embodiments 1-3, and the material has good electrochemical stability under a high cut-off voltage of 4.5V.
The above description is not intended to limit the present invention, and the present invention is not limited to the above embodiments. Those skilled in the art should also realize that changes, modifications, additions and substitutions can be made without departing from the spirit and scope of the invention.
Claims (10)
1. A single crystal shaped ternary anode material for lithium ion battery with LiNi as its chemical general formula x Co y Mn 1-x-y A a O 2 Wherein x is more than or equal to 0.5<1，0<y≤0.5，0<x+y≤0.5，0<a is less than or equal to 0.01, and A is at least one of additive modified elements Mg, Ca and Sr; the median particle diameter D50 of the single-crystal-morphology lithium ion battery ternary positive electrode material is 1-10 mu m.
2. The lithium ion battery ternary cathode material with the single crystal morphology according to claim 1, wherein the median particle diameter D50 of the lithium ion battery ternary cathode material with the single crystal morphology is 3-5 μm.
3. The preparation method of the single-crystal-morphology lithium ion battery ternary cathode material according to claim 1 or 2, comprising the following steps:
1) preparing a metal salt solution: weighing nickel salt, cobalt salt and manganese salt according to the molar ratio x: y (1-x-y), dissolving the nickel salt, cobalt salt and manganese salt in deionized water, and uniformly mixing to obtain a metal salt solution; preparing a precipitator, an additive solution and a base solution;
2) pumping the metal salt solution, the precipitating agent and the additive solution in the step 1) into the substrate in the step 1), reacting at a proper temperature, pH and stirring speed, and after the reaction is finished, aging, washing and drying to obtain a carbonate precursor Ni x Co y Mn 1-x-y A a CO 3 ；
3) The carbonate precursor Ni prepared in the step 2) is added x Co y Mn 1-x-y A a CO 3 Uniformly mixing with a lithium source, sintering in an oxygen atmosphere furnace, cooling, grinding, crushing and sieving to obtain the lithium ion battery ternary cathode material LiNi with single crystal morphology x Co y Mn 1-x- y A a O 2 。
4. The preparation method of the single-crystal-morphology lithium ion battery ternary cathode material according to claim 3, characterized in that in the step 1), the nickel salt is at least one of nickel sulfate, nickel nitrate and nickel chloride; the cobalt salt is at least one of cobalt sulfate, cobalt nitrate and cobalt chloride; the manganese salt is at least one of manganese sulfate, manganese nitrate and manganese chloride; the total concentration of metal cations in the metal salt solution is 0.5-2.0 mol/L.
5. The preparation method of the single-crystal-morphology lithium ion battery ternary cathode material according to claim 3, wherein in the step 1), the precipitant is 1-3 mol/LNa 2 CO 3 、NH 4 HCO 3 And NH 3 ·H 2 One or a mixture of O solution, wherein the mixture is composed of Na with the concentration of 1-3 mol/L 2 CO 3 、NH 4 HCO 3 And NH 3 ·H 2 The O solution is composed of 1-200: 1-200 by volume ratio; the additive is chloride salt of a modifying element A, and the chloride salt of the modifying element A is MgCl 2 、CaCl 2 And SrCl 2 At least one additive, wherein the concentration of the additive is 0.01-1 mol/L; the base solution is composed of deionized water and NH with the concentration of 1-3 mol/L 4 HCO 3 And NH 3 ·H 2 The O solution is prepared according to the volume ratio of 1-200: 1-200.
6. The preparation method of the single-crystal-morphology lithium ion battery ternary cathode material according to claim 3, characterized in that in the step 2), the pumping speeds of the metal salt solution, the precipitant and the additive solution are respectively 1-100 mL/min, the pumping time is the same as the reaction time, and the metal salt solution, the precipitant and the additive solution are continuously pumped in the reaction time; the reaction temperature is 30-60 ℃, the pH value is 7-9, the stirring speed is 300-900 r/min, the reaction time is 8-48 h, the aging time is 6-16 h, the mixture is washed by deionized water at 50-90 ℃, the drying temperature is kept at 60-150 ℃, and the drying time is 6-20 h.
7. The method for preparing the single-crystal-morphology lithium ion battery ternary cathode material according to claim 3, wherein Ni in the step 2) is adopted x Co y Mn 1-x-y A a CO 3 The content a of the additive element A is 0.001-0.01.
8. The method for preparing the ternary cathode material of the lithium ion battery with single crystal morphology according to claim 3, wherein in the step 3), the lithium source is at least one of lithium carbonate, lithium hydroxide and lithium nitrate; carbonate precursor Ni x Co y Mn 1-x-y A a CO 3 The molar ratio of the Li/(Ni + Co + Mn) in the lithium source to the Li/(Ni + Co + Mn) is 1.00-1.10; carbonic acidSalt precursor Ni x Co y Mn 1-x-y A a CO 3 Mixing the lithium source and the lithium source in a high-speed mixer at a rotating speed of 400-800 r/min for 30-60 min.
9. The preparation method of the single-crystal-morphology lithium ion battery ternary cathode material according to claim 3, wherein in the step 3), the sintering process is as follows: the temperature rising speed is 1-10 ℃/min, the first-stage sintering temperature is 500-700 ℃, and the sintering time is 4-10 h; and then the temperature is raised to the second-stage sintering temperature of 800-1000 ℃, and the sintering time is 8-14 h.
10. The use of the single crystalline morphology lithium ion battery ternary positive electrode material of claim 1 in a lithium ion battery.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106159251A (en) * | 2015-03-31 | 2016-11-23 | 河南科隆新能源有限公司 | One kind monocrystalline lithium battery tertiary cathode material and preparation method thereof |
| CN106654197A (en) * | 2016-11-28 | 2017-05-10 | 荆门市格林美新材料有限公司 | Preparation method of ternary precursor containing Mg and Al |
| CN106784686A (en) * | 2016-12-21 | 2017-05-31 | 烟台卓能电池材料股份有限公司 | A kind of doped lithium ion battery class monocrystalline multicomponent material and preparation method thereof |
| CN109811412A (en) * | 2018-12-28 | 2019-05-28 | 广东邦普循环科技有限公司 | A kind of stratiform nickel lithium manganate cathode material of monocrystalline pattern and preparation method thereof |
| CN110931768A (en) * | 2019-11-17 | 2020-03-27 | 新乡天力锂能股份有限公司 | Ternary positive electrode material of high-nickel monocrystal lithium ion battery and preparation method |
| CN112018372A (en) * | 2020-07-16 | 2020-12-01 | 北京泰丰先行新能源科技有限公司 | Single-crystal ternary cathode material, preparation method thereof and lithium ion battery |
| CN113644262A (en) * | 2021-07-21 | 2021-11-12 | 格林美（无锡）能源材料有限公司 | Layered large-particle-size high-nickel single crystal ternary cathode material and preparation method thereof |
| CN114162881A (en) * | 2021-11-26 | 2022-03-11 | 中国长江三峡集团有限公司 | Preparation method of anion in-situ doped high-nickel ternary cathode material |
-
2022
- 2022-06-08 CN CN202210645933.0A patent/CN114843504A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106159251A (en) * | 2015-03-31 | 2016-11-23 | 河南科隆新能源有限公司 | One kind monocrystalline lithium battery tertiary cathode material and preparation method thereof |
| CN106654197A (en) * | 2016-11-28 | 2017-05-10 | 荆门市格林美新材料有限公司 | Preparation method of ternary precursor containing Mg and Al |
| CN106784686A (en) * | 2016-12-21 | 2017-05-31 | 烟台卓能电池材料股份有限公司 | A kind of doped lithium ion battery class monocrystalline multicomponent material and preparation method thereof |
| CN109811412A (en) * | 2018-12-28 | 2019-05-28 | 广东邦普循环科技有限公司 | A kind of stratiform nickel lithium manganate cathode material of monocrystalline pattern and preparation method thereof |
| CN110931768A (en) * | 2019-11-17 | 2020-03-27 | 新乡天力锂能股份有限公司 | Ternary positive electrode material of high-nickel monocrystal lithium ion battery and preparation method |
| CN112018372A (en) * | 2020-07-16 | 2020-12-01 | 北京泰丰先行新能源科技有限公司 | Single-crystal ternary cathode material, preparation method thereof and lithium ion battery |
| CN113644262A (en) * | 2021-07-21 | 2021-11-12 | 格林美（无锡）能源材料有限公司 | Layered large-particle-size high-nickel single crystal ternary cathode material and preparation method thereof |
| CN114162881A (en) * | 2021-11-26 | 2022-03-11 | 中国长江三峡集团有限公司 | Preparation method of anion in-situ doped high-nickel ternary cathode material |
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